Alkyl trialkylammonium salts as disperse dyes for acrylic fibers



(1 -ALKYLAMINO 6 (7) ANTHRAQUINONYL- SULFONAMIDO)ALKYL TRIALKYLAMMONIIMSALI'IIS AS DISPERSE DYES FOR ACRYLIC FIB RS Asa Willard Joyce,Plainfield, N. assign'or to American Cyanamid Company, New York, N.Y., acorporation 'of Maine No Drawing. Original application Sept. 25, 1957,Ser. No. 686,048. Divided and this application Aug. 4, 1958, Ser. No.753,124

8 Claims. (Cl. 260-371) .the said amino group being, when not freeamino, substituted by an aliphatic group which, when not lower alkyl, iscyclohcxyl; the said sulfonamide group being a substituted sulfonamidein which the substituting group is a quaternary ammonium alkylene group,the said quaternary ammonium group having three substituents, at leasttwo of which are lower alkyl and the other, when not lower alkyl, beingcyclohexyl.

This application is a division of my copending applicaton, Serial No.686,048, filed September 25, 1957, now abandoned.

The polyacrylonitrile fibers, which have become increasingly usefularticles of commerce, are diflicult to dye. Most of the commerciallyavailable fibers of this type contain a major proportion ofpolyacrylonitrile. In most cases over 85% of the fiber is acrylonitrile.Few of the standard dyestuffs available show afiinity for these highacrylonitrile content fibers. Especially it has been hard to obtain deepshades on these fibers since deep shades require a strong aifinity ofthe fiber for the dyestuif. The only way to achieve deep shades has beento increase the time and temperatures of the dyeing process. Suchdrastic conditions of dyeing result in injury to the fabrics. Theresistant properties of these fibers are desirable for general textileuse because they render the fiber physically durable. However, theproblem of dyeing has been so great that these durable types may have tobe superseded by more dyeable types which are less durable physicallyunless methods of-dyeing them readily are found. The usual disperse dyeshave little or no aflinity for fibers made of polyacrylonitrile. Thosebasic dyes which do dye fibers of this type give dyes of poor fastnessto light and in addition, such dyes usually need dispersing orsolubilizing agents to form the dyebath.

I have found, that cationic anthraquinone dyes of the.

formula:

R",NH h) V /R V SO2-NH-(CH2)-ll A- R R r t in which R" is hydrogen oralkyl of less than seven carbon atoms, R is lower alkyl, R is loweralkyl or cyclohexyl; n is an integer from 2 to 4 and A- is an anion,have excellent affinity for polyacrylonitrile fibers with major ingly'soluble in water, dyeing acrylic fibers with major proportion ofacrylonitrile with great ease by the usual disperse methods.

The dyes of my invention are usually prepared from 2,938,914 PatentedMay 31,

2 l-nitro-6-anthraquinonesulfonyl chloride, 1 nitro 7anthraquinonesulfonyl chloride or mixtures of the two isomers. Thesulfonyl chloride group is reacted with an alkylated alkylene diamineafter which the nitro group is replaced by an amino or a substitutedamino. The quaternizable dye thus formed is then quaternized to form thecationic anthraquinone disperse dyes of my invention. These reactionscan be shown by the following equation:

can be placed on the amino group, such as propyl butyl and hexyl.Similarly, the alkyl groups need not' be the same so that one can usemethylethylaminoethylamine o methylethylaminopropylamine and the like.

Thenitro group may be replaced with ammonia to give the free amine orwith a lower alkyl amine such as methylamine, ethylamine, butylamine,isobutylamine, isopropylamine, tert-butylamine or with cyclohexylamine.The quaternization is eifected by reaction with a compound of thegeneral formula RA in which R is the quaternizing group and A is theanion which may contain an alkyl or other organic residue. The followingquaternizing agents may be used: dialkyl sulfates, such as dimethylsulfate, diethyl sulfate, dipropyl sulfate or dibutyl sulfate; alkylhalides such as methyl iodide, ethyl iodide, methyl chloride, ethylchloride, butyl bromide, hexyl bromide, and the like, aralkyl halidessuch as benzyl chloride, phenylethylbromide and the like or alkyl estersof aryl sulfonic acids such as the methyl, ethyl, propyl or butyl estersof para-toluene sulfonic acid or substituted alkyl halides such asethylene chlorohydrin, propylene chlorohydrin and the like, or alkenylhalides such as alkyl brornide Usually it is preferredthat thequatemizingagents contain the lower alkyl groups such as methyl andethyl, as these are the preferred guaternizing groups.

Polyacrylonitriles which may be dyed with the compound of my invention.and which fall within the scope of my invention are those polymers andcopolymers of acrylonitrile which contain a major proportion by weightof acrylonitrile, they may also contain basic comonomers as methyl vinylpyridine and vinyl pyridine or comonomer-s such as methyl acrylatc,vinyl acetate and vinyl chloride. .Of the polyacrylonitriles availablecommercially which can be used to form the colored polyacrylonitriles ofmy invention, one is 100% polyacrylonitrile, another is approximately95% acrylonitrile and approximately 5% methyl acrylate, another'has 89%of acrylonitrile, 6% methyl vinyl pyridine and 5% vinyl acetate, andstill another has a composition of 94% acrylonitrile, 5% methyl vinylpyridine and 1% vinyl acetate. Polymers having as little as 50%acrylonitrile can be dyed by the class of dyes of my invention to formthe dyed fibers of my invention.

It is an advantage of my invention that the new dyes which I haveinvented are surprisingly soluble in water and dye acrylic fibers havinga major proportion of acrylonitrile with ease by the usual dispersedyeing methods. The preferred method of application is at the boil in anaqueous dye bath which is neutral to weakly alkaline, although fiberscan also be dyed in an acidic medium.

It is a further advantage of our invention that the dyes are orange .redto red violet shades of good fastness to washing. For example, thedyestuff of the formula:

a s- 1 l Example 1 Cfil -NH CH1 Oa-NH-OH1OHg-CHr-N CHaSOr I CH: 0

To 10.6 parts of 1-nitro-6-anthraquinony1sulfonyl chlo- 4aminopropylaminosulfonyl anthraquinone thus prepared is further purifiedby grinding to a smooth paste with water, diluting with parts of waterand adjusting the alkalinity with about 3 parts by weight of sodiumcarbonate until alkaline to phenolphthalein indicator paper. Afterstirring in this alkaline medium, the product isagain isolated byfiltration, washed free from alkali with water, followed by a smallmethanol wash, and dried.

A mixture of 6.3 parts by weight of the above product, 75 parts byvolume of toluene, and 4.1 parts by volume of 70% ethylamine isgradually warmed to C. The mixture is heated at 85-95 C. until thereaction is complete. The partially precipitated product is isolated byevaporation and dried. The product is l-ethylamino-6-dimethylaminopropylaminosulfonyl anthraquinone.

3.1 parts of the above product is dissolvedin parts I by volume oforthodichlorobenzene by heating at reflux. The solution is then cooledto 50 C. and 1.35 parts of dimethyl sulfate solution added. The reactionmixture 7 C. for a shorttime (one half hour when parts are grams), andthen held at about 85 C. until quaternization is complete. The mixtureis then cooled to 50 C. and the product is isolated by filtration. It isthen ground and reslurried in orthodichloro benzene and again filteredand washed with orthodichlorobenzene, followed by benzene, and dried.The product has the above structure.

is then warmed to 100 Example 2 CzHs-NH O I H CH5 SOz-NHCH CHrCHrN I HCH: 0

2.7 parts of the product of Example 1 in 100 parts by volume of waterare treated with 10 parts of potassium iodide. The sulfate anion is thusreplaced by an iodide anion. The product is isolated by filtration.

If in Example 1 the ethylamine is replaced with 1.4 parts ofmethylamine, a corresponding cationic anthraquinone dyestuflf of theabove formula is obtained which dyes polyacrylonitrile fibers having ahigh acrylonitrile content reddish-violet shades.

Example 4 CHaCHzCILCHg-NH 0 02H soiNn-omomomonr-r r cnnsor i 1 02 5 010.6 parts of 1-nitro-G-anthraquinonylsulfonyl chloride are slurried in75 parts by volume of benzene. To this is added 8.7 parts ofdiethylaminobutylamine and the 70 mixture warmed at 50 C. until reactionis complete.

The product (1-nitro-6-diethylaminobutylaminosulfonyl anthraquinone) isisolated by filtration and washed with benzene.

This product is then mixed with parts by volume of 75 toluene and 7.3parts of butylamine is added. The mixa ma ture is heated at 85-95 C.until the nitro group is substantially replaced by butylamino groups.The product is isolated by evaporation.

The product obtained (l-butylamino-G-diethylaminobutylaminosulfonylanthraquinone) is added to 200 parts by volume of orthodichlorohenzeneand heated at reflux until dissolved. To this solution is added 6.1parts of diethyl sulfate and the mixture is heated at 85 C. untilquaternization is complete. The product of the formula above is thenisolated by filtration, washed with orthodichlorobenzene and dried. Itdyes acrylonitrile polymers, both those with basic comonomers and fromweakly alkaline baths, reddishwiolet shades.

To 10.6 parts of 1-nitro-6-anthraquinonylsulfonyl chloride in 75 partsby volume of benzene at 15-20 C. is added 5.3 parts ofdimethylaminoethylamine in 25 parts by volume of benzene. The mixture iswarmed at 50 C. until replacement of the chlorine in complete. Thereaction mixture is then cooled, filtered and the product Washed withbenzene and dried.

The product is added to 150 parts by volume of toluene. To this is added8.9 parts of cyclohexylamine and the mixture heated at 85-95 C. untilthe nitro group is substantially replaced with a cyclohexylamino group.The product is isolated by evaporation and quaternized using an excess(about 2.6 parts) of ethyl chloride, using the solvent andquaternization method of Example 4. The reaction mixture is cooled to 50C. and filtered. The product is washed with orthodichlorobenzene anddried. It dyes acrylic fibers having a high acrylonitrile contentreddish-violet shades.

Example 6 Chin-NH I ll SOBNHmmcHZGm-FJ omso;

. CHs CH: (lg

If in Example 1, 10.6 parts of 1-nitro-6-anthraquinony1- sulfonylchloride are replaced by the same amount of1-nitro-7-anthraquinonylsulfonyl chloride, 21 water soluble cationicdyestutf is obtained which dyes Orlon a violet shade, which is somewhatredder than the dye produced in Example 1.

Example 7 H: The procedure of Example 1 is followed except that thesecond step (replacement of the nitro group by ethylamine) is carriedout in o-dichlorobeuzene instead of toluene (in equal amount) by passingammonia gas through the solution, the mixture being held at 160 C. andthe ethylamine being omitted. The final product is the dye of the abovestructure which dyes acrylic fibers a bright orange red.

Example 9 Acrylic fibers may be dyed with the dyes of the preced ingexamples by the following preferred procedure: To a dye bath is added apiece of acrylic cloth consisting of between -l00% acrylonitrile plus 40parts of water per unit weight of the fabric and one part by weight ofthe dyestuff of Example 1 and 1 part by weight of sodium carbonatesolution. The dye bath is boiled for 1 hour at the end of which time thecloth is removed, rinsed and dried. A reddish-violet shade of good Washfastness is obtained.

If a fabric composed of acrylonitrile and 5% methyl acrylate is used, asimilar result is obtained. Also, a similar but slightly deeper shade isobtained with a fiber consisting of 88.7% acrylonitrile, 6.3% methylvinyl pyridine and 5% vinyl acetate.

Example 10 C2H5NH O CHa SO2NH-CH2CHzCH -N CHgSO; CH: 0

re r r CH2 CH The procedure of Example 1 is followed except thatmethylcyclohexylaminopropylamine is used in equivalent quantity insteadof dimethylaminopropylamine.

I claim:

1. Alpha-amino anthraquinone beta sulfonamides having no other ringsubstituents in which the amino group is on a different ring from thesulfonamide; the said amino group being selected from the groupconsisting of free amino groups, amino groups substituted by lower alkylradicals and amino groups substituted by a cyclohexyl radical; the saidsulfonamide group being a substituted sulfonamide in which thesubstituting group is a quaternary ammonium alkylene group, the saidquaternary ammonium group having three substituents selected from thegroup consisting of lower alkyl and cyclohexyl, at least two of whichare lower alkyl.

2. [3 (1 ethylamino 6anthraquinonylsulfonamido)-propyl]-trimethylammonium methyl sulfate.

3. [3 (1 ethylamino 6 anthraquinonylsulfonamido) propyl]-trimethylammonium iodide.

4. [3 (1 methylamino 6 anthraquinonylsulfonamido) -propyl]-trimethylammonium methyl sulfate.

5. [4 (1 butylamino 6 anthraquinonylsulfonamido) -butyl]-triethylammonium ethyl sulfate.

6. [2 (1 cyclohexylamino 6 anthraquinonylsulfonamido) -ethyl]-ethyldimethyl ammonium chloride.

7. [3 (1 ethylamino 7 anthraquinonylsulfonamido) -propyl]-trimethylammonium methyl sulfate.

8. [3 (1 amino 6 anthraquinonylsulfonamido)- propyll-trimethylammoniummethyl sulfate.

References Cited in the file of this patent UNITED STATES PATENTS2,371,101 Kienle et a1 Mar. 6, 1945 FOREIGN PATENTS 1,140,531 FranceMar. 4, 1957 Patent should f major" read fibers and are surpris- UNITEDSTATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2,338,914 May31, 1960 Asa Willard Joyce It is hereby certified the t error appears inthe printed specification of the above numbered patent re quiringcorrection and that the said Letters readas corrected below.

Column 1, fourth line below the formula for "fibers with Signed andsealed this 1st day of November 1960.

SEAL) ttest: ARL H. AXLINE ROBERT C. WATSON ttesting OflicerCommissioner of Patents

1. ALPHA-AMINO ANTHRAQUINONE BETA SULFONAMIDES HAVING NO OTHER RINGSUBSTITUENTS IN WHICH THE AMINO GROUP IS ON A DIFFERENT RING FROM THESULFONAMIDE, THE SAID AMINO GROUP BEING SELECTED FROM THE GROUPCONSISTING OF FREE AMINO GROUPS, AMINO GROUPS SUBSTITUTED BY LOWER ALKYLRADICALS AND AMINO GROUPS SUBSTITUTED BY A CYCLOHEXYL RADICAL, THE SAIDSULFONAMIDE GROUP BEING A SUBSTITUTED SULFONAMIDE IN WHICH THESUBSTITUTING GROUP IS A QUATERNARY AMMONIUM ALKYLENE GROUP, THE SAIDQUATERNARY AMMONIUM GROUP HAVING THREE SUBSTITUENTS SELECTED FROM THEGROUP CONSISTING OF LOWER ALKYL AND CYCLOHEXYL, AT LEAST TWO OF WHICHARE LOWER ALKYL.